Insecticidal use of phosphorus containing oxime carbamates

ABSTRACT

A METHOD OF CONTROLLING INSECTS WHICH COMPRISES CONTACTING SAID INSECTS WITH AN INSECTICIDALLY EFFECTIVE QUANTITY OF A COMPOUND HAVING THE FORMULA   (Q,(R3-O-N=C(-R2)-)PHENYL)-O-P(=X)(-R)-R1   IN WHICH X IS SELECTED FROM THE GROUP CONSISTING OF OXYGEN AND SULFUR; R IS SELECTED FROM THE GROUP LOWER ALKYL OR LOWER ALKOXY, HAVING FROM 1 TO 6 CARBON ATOMS, INCLUSIVE; R1 IS SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL, LOWER ALKOXY HAVING FROM 1 TO 6 CARBON ATOMS, INCLUSIVE, AMINO, LOWER ALKYL-SUBSTITUTED AMINO AND PHENYL; Q IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, DIVALENT TETRAMETHYLENEDIENE-1,3,LOWER ALKOXY OR LOWER ALKYL HAVING FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, NITRO, AND HALOGEN; AND LOWER DIALKYL SUBSTITUTED THIONOPHOSPHORYLOXY; R2 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL HAVING FROM 1 TO 4 CARBON ATOMS AND PHENYL; R3 IS A CARBAMATE   -CO-N(-R5)-R6   IN WHICH R5 AND R6 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN; ALKYL HAVING FROM 1 TO 10 CARBON ATOMS, INCLUSIVE, SUBSTITUTED ALKYL HAVING 1 TO 6 CARBON ATOMS, INCLUSIVE, SAID SUBSTITUENT IS SELECTED FROM THE GROUP CONSISTING OF HYDROXY, HALOGEN, AMINO, DILOWER ALKYLAMINO, AND LOWER ALKOXY; LOWER ALKENYL HAVING FROM 2 TO 4 CARBON ATOMS, INCLUSIVE; CARBOALKOXY ALKYL HAVING A TOTAL OF FROM 3 TO 8 CARBON ATOMS, INCLUSIVE; CYCLOALKYL HAVING FROM 3 TO 6 CARBON ATOMS, INCLUSIVE; PHENYL; NAPHTHYL; SUBSTITUTED PHENYL WHEREIN SAID SUBSTITUENTS ARE SELECTED FROM THE GROUP CONSISTING OF HALOGEN, LOWER ALKYL, LOWER ALKOXY, LOWER THIOALKYL, LOWER DIALKYLAMINO IN WHICH SAID LOWER ALKYL AND LOWER ALKOXY MOIETIES HAVING FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, NITRO, CYANO, TRIFLUOROMETHYL AND COMBINATIONS THEREOF.

United States Patent 3,769,419 INSECTICIDAL USE OF PHOSPHORUS CONTAIN-ING OXIME CARBAMATES Arnold D. Gutman, Pinole, Calif., assignor toStaufier Chemical Company, New York, N.Y.

No Drawing. Application May 20, 1968, Ser. No. 730,588, which is acontinuation-in-part of application Ser. No. 646,467, June 16, 1967,both now abandoned. Divided and this application June 25, 1970, Ser. No.59,845

Int. Cl. A01n 9/36 US. Cl. 424-211 38 Claims ABSTRACT OF THE DISCLQSUREA method of controlling insects which comprises contacting said insectswith an insecticidally effective quantity of a compound having theformula Q at /PO /R2 R1 C=NOR3 in which X is selected from the groupconsisting of oxygen and sulfur;

R is selected from the group lower alkyl or lower alkoxy,

having from 1 to 6 carbon atoms, inclusive;

R is selected from the group consisting of lower alkyl,

lower alkoxy having from 1 to 6 carbon atoms, inclusive, amino, loweralkyl-substituted amino and phenyl;

Q is selected from the group consisting of hydrogen, divalenttetramethylenediene-1,3,lower alkoxy or lower alkyl having from 1 to 4carbon atoms, inclusive, nitro, and halogen; and lower dialkylsubstituted thionophosphoryloxy;

R is selected from the group consisting of hydrogen, lower alkyl havingfrom 1 to 4 carbon atoms and phenyl;

R is a carbamate in which R and R are independently selected from thegroup consisting of hydrogen; alkyl having from 1 to 10 carbon atoms,inclusive, substituted alkyl having 1 to 6 carbon atoms, inclusive, saidsubstituent is selected from the group consisting of hydroxy, halogen,amino, dilower alkylamino, and lower alkoxy; lower alkenyl having from 2to 4 carbon atoms, inclusive; carboalkoxy alkyl having a total of from 3to -8 carbon atoms, inclusive; cycloalkyl having from 3 to 6 carbonatoms, inclusive; phenyl; naphthyl; substituted phenyl wherein saidsubstituents are selected from the group consisting of halogen, loweralkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in which saidlower alkyl and lower alkoxy moieties having from 1 to 4 carbon atoms,inclusive, nitro, cyano, trifluoromethyl and combinations thereof.

This application is a division of copending application Ser. No. 730,588filed May 20, 1968, now abandoned, which in turn was acontinuation-in-part of then copending application Ser. No. 646,467,filed June 16, 1967, now abandoned.

This invention relates to certain novel phosphorus containing compoundswhich can be used as insecticides, animal parasiticides, both contactand systemic, herbicides and foliage fungi protectants. Morespecifically, this invention relates to certain substituted organo-oximephos- 3,769,419 Patented Oct. 30, 1973 ice in which X and Y areindependently selected from the group consisting of oxygen and sulfur; Ris selected from the group lower alkyl or lower alkoxy, each having from1 to 6 carbon atoms, inclusive; R is selected from the group consistingof lower alkyl having from 1 to 6 carbon atoms, inclusive or loweralkoxy having from 1 to 6 carbon atoms, inclusive, amino, loweralky1-substituted amino, and phenyl; Q is selected from the groupconsisting of divalent tetramethylenediene-1,3, lower alkoxy or loweralkyl having from 1 to 4 carbon atoms inclusive, each, nitro, halogenand combinations thereof, and lower dialkyl substituted thiophosphoryl;R is selected from the group consisting of hydrogen, lower alkyl havingfrom 1 to 4 carbon atoms and phenyl; and R is selected from the groupconsisting of hydrogen, substituted carbonate and thiocarbonates of thetype 0 i JZ'R4 in which Z is oxygen or sulfur, R is lower alkyl havingfrom 1 to 4 carbon atoms, inclusive, and ,B-chloroloweralkyl having from2 to 4 carbon atoms; carbamates of the type in which R and R areindependently selected from the group consisting of hydrogen, alkylhaving from 1 to 10 carbons, inclusive, substituted alkyl having 1 to 6carbon atoms inclusive, said substituent is selected from the groupconsisting of hydroxy, halogen, amino, di-lower alkyl amino, loweralkoxy and tetrahydrofuryl; lower alkenyl having from 2 to 4 carbons,inclusive, carboalkoxy alkyl having a total of from 3 to 8 carbon atoms,inclusive, cycloalkyl having from 3 to 6 carbon atoms, inclusive,piperazino, Z-thiazolyl phenyl, naphthyl, substituted phenyl whereinsaid substituents are selected from the group consisting of halogen,lower alkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in whichsaid lower alkyl and lower alkoxy moieties have from 1 to 4 carbonatoms, inclusive, nitro, cyano and trifluoromethyl; and in which e is anN-containing heterocyclic member selected from the group consisting ofmorpholino, piperazino, pyrrolidinO, piperadino, hexamethyleneimino,pyrr'yl, indolyl, imidazolyl, benzimidazoly, pyrazolyl, 1,3-oxazolidino,and 1,3-thiazolidino; esters of the type (|!}R1 wherein R is selectedfrom the group consisting of alkyl having from 1 to 8 carbons, inclusivetrichloromethyl and lower alkenyl having from 2 to 4 carbon atoms,inclusive, and the radical (CH -SR in which in is l or 2, R is alkylhaving 1 to 6 carbon atoms, alkenyl having 2 to 4 carbon atoms, phenyl,substituted phenyl in which said substituents are selected from thegroup halogen, lower alkyl having 1 to 4 carbon atoms, inclusive andlower alkoxy having 1 to 4 carbon atoms, inclusive; lower alkylsulfonato having from 1 to 6 carbon atoms, inclusive; lower alkylsubstituted thiophosphoryl wherein the lower alkyl groups independentlycontain from 1 to 4 carbon atoms, inclusive; and2,2,2-trichloro-1-hydroxyethyl-4- cyanophenyl, 2,4,5-trichlorophenyl and4-methylthiophenyl. Lower alkyl and lower alkoxy includes those membersof the groups which contain the indicated number of carbon atoms in bothstraight chain and branched chain configurations. Lower alkenyl includesthose members of the group containing a double bond and containing from2 to 4 carbon atoms, inclusive. When Q is divalent tetramethylene1,3 itis bonded to the 2,3 or 3,4- carbon atoms of the phenyl ring, therebybecoming either aor ,B-naphthyl, respectively. Also included herein is amethod of preparing, using, and applying the compositions.

The compounds herein described can be prepared by several methods. Onesuch general method applicable in preparing the compounds is thecondensation between the appropriate substituted phosphorus-containingoxy or thio benzaldehyde, e.g. phosphoro, phosphono, and phosphino, andhydroxylamine hydrochloride in order to prepare the correspondingbenzaldoxime. The benzaldoxime can be further reacted with appropriatesubstituted isocyanate, substituted acid chlorides, substituted chloroformate, substituted chlorothiolformate, substituted sulfonyl chloride,monosubstituted carbamyl chloride, N,N- dissubstituted carbamylchloride, substituted phosphoryl chloride, substituted thionophosphorylchloride, or anhydrous trichloro-acetaldehyde. When R is to be loweralkyl, an appropriate substituted-phosphoryl orsubstitutedthiophosphoryl lower alkyl phenylketone is condensed withhydroxylamine hydrochloride to prepare the corresponding ketoxime.Another method useful for the preparation of carbamyl derivatives isfirst the condensation of phosgene with the aldoxime followed by thecondensation with a primary or secondary amine. The reactions proceedreadily in the liquid phase. The employment of a solvent is also useful,facilitating processing, as well as agitation of the reactants. Solventssuch as water, benzene, toluene, chloroform, aqueous ethanol and thelike, can be employed. When using derivatives containing the aldoxime,it is preferred to carry out the reaction in the presence of a hydrogenhalide acceptor such as sodium carbonate, triethylamine, pyridine,picoline and the like, which are use as catalyst. Similarly, in thecondensation reaction to prepare secondary carbamyl derivatives, thereaction is preferably conducted in the presence of a hydrogen halideacceptor.

The reactions are carried out at temperatures that permit operation inthe liquid phase. These temperatures are between about room temperatureand reflux temperature of the solvent, if one is employed. preferably,the reaction mixture is refluxed, usually at an elevated temperature.The ketoxime can be reacted with function moieties as described suprafor the benzaldoxime.

It now has been discovered that the new compositions disclosed hereinare distinguished as useful as insecticides, herbicides, follar fungiprotectants and are particularly effective as systemic porasiticidalagents for animals.

The compounds of the present invention are prepared in accordance withthe following illustrative examples.

EXAMPLE 1 Preparation of the intermediate3-[O-(0,0-diethylphosphorothioyl)] benzaldehyde In 200 ml. of methylethyl ketone in a 500 ml. S-neck flask are combined 24.4 g. (0.2 moles)3-hydroxybenzaldehyde, 37.8 g. (0.2 moles)0,0-diethylthiophosphorylchloride, and 16.4 g. (0.12 moles) potassiumcarbonate. The mixture is stirred and heated ll dfi I fluX for 4 hours,

4 cooled, and poured into 300 ml. of water. The mixture is filtered freeof solid and is extracted with two 150 ml. portions of chloroform. Thechloroform phases are combined, dried with anhydrous MgSO and thesolvent evaporated. There is obtained 54.7 g. (99.5 percent of theory)of the title intermediate, n =1.5239.

Preparation of 3-[0,0-diethylphosphorothioyl] bzenzaldoxime In 300 ml.of water are combined 27.4 g. (0.1 mole)3-[O-(0,0-diethylphosphorothioyl)] benzaldehyde and 7.6 g. (0.1 mole)hydroxylamine hydrochloride. The mixture is stirred at room temperature,and 7.5 g. (0.06 mole) sodium carbonate monohydrate is added over aperiod of 20 min. The resulting mixture is stirred at room temperaturefor 1 hour. The mixture is extracted with two 150 ml. portions ofbenzene. The benzene phases are combined, dried with anhydrous MgSO andevaporated. There is obtained a yield of 20.0 g. (68.3% of theory) oftitle compound, n =1.546O.

EXAMPLE 2 Preparation of 3- [O- (0,0-diethylphosphorothioyl)benzaldoximino-N-methyl carbamate Ten grams (0.034 mole) of3-[O-(O-diethylphosphorothioyl) ]-benzaldoxime dissolved in 10 m1. ofacetone is treated with an excess of methylisocyanate. The mixture ispoured into 200 ml. of benzene. The benzene is washed with two 50 ml.portions of water, dried with anhydrous MgSO and evaporated. There isobtained a yield of 11.2 g. (93.3 percent of theory) of the titlecompound, n =1.5394.

EXAMPLE 3 Preparation of 4-[0-(0,0-diethylphosphorothioyl)1-acetophenone oxime In 150 ml. of percent aqueous ethanol are combined56.2 g. (0.195 mole) 4-[O-(0,0-diethylphosphorothioy1)]-acetophenone,17.4 g. (0.25 mole) hydroxylamine hydrochloride, and 4 guns. (0.1 mole)sodium hydroxide. The mixture is heated and refluxed for 5 min., cooled,acidified with concentrated hydrochloride acid and extracted with twoml. portions of chloroform. The chloroform phases are combined, driedwith anhydrous MgSO and evaporated. There is obtained 55.0 g. (93.5percent of theory) of the title compound, n =1.5393.

EXAMPLE 4 Preparation of 4- [O- (0,0-diethylphosphorothioyl)acetophenoneoxime-N-methyl carbarnate By an analogous procedure as givenin Example 2, supra, 10.0 g. (0.03 mole) of4-[O-(0,0-diethylphosphorothioyl)Jacetophenoneoxime is reacted withmethyl isocyanate. There was obtained 11.5 g. (96.9 percent of theory)of the title compound.

EXAMPLE 5 Preparation of 4-[0,0-diethylphosphorothioyl]-acetophenoneoximino acetate The following procedure also can be usedwith a carbamyl chloride, sulfonyl chloride or chloroformate in order toobtain compounds that include the respective functional moieties typicalof said reactants.

In 150 ml. of benzene 10.0 g. (0.03 mole) of 4-[4- (0,0diethylphosphorothioyl)] acetophenoneoxime, 3.2 g. (0.04 mole) ofacetylchloride, and 4.1 g. (0.04 mole) of triethylamine are combined.The mixture is heated and refluxed for about one hour. The cooledreaction mixture is washed with two 50 ml. portions of water. Thebenzene phase is dried With anhydrous magnesium sulfate and then thebenzene evaporated. There is obtained 11.0 g. (96.5 percent of theory)of the title compound n =l.5279.

EXAMPLE 6 Preparation of 4-[O-(O,O-diethylphosphorothioyl)]benzaldoximino-N'-morpholinylcarbamate Seven grams (0.07 mole) ofphosgene in 150 ml. of anhydrous diethyl ether is added to a 500 ml.3-neck flask fitted with a stirrer, dropping funnel, Dry Ice condenser,and thermometer. The solution is stirred and cooled to 10 C. with an icebath. N,N-dimethylaniline, 8.6 g. (0.07 moles) is added over a period of30 minutes. 4-[O(0,0- diethylphosphorothioyl)] benzaldoxime, 14.5 g.(0.05 mole) in 50 ml. of anhydrous diethyl ether is added over a periodof 30 min. The temperature of the reaction mixture is maintained between10 and C. After the addition is complete, the mixture is stirred for onehour at 15 C. A solution of 17.4 grams (0.2 mole) of morpholine and 10ml. of water is added to the stirring reaction mixture at such a ratethat the temperature does not exceed 15 C. After the addition iscomplete, the mixture is stirred for two hours at room temperature. Themixture si diluted with 200 ml. of ether and Washed consecutively with100 ml. of water, 100 ml 1 N HCl, and again with 100 ml. of water. Theether phase is dried with anhydrous MgSO and evaporated to yield 18grams (89.8% of theory) of 4-[O-(0,0-diethylphosphorothioyl)]benzaldoximino N morpholinylcarbamate, n =1.5423.

EXAMPLE 7 Preparation of 4[0 (0,0-diethylphosphorothioyl)1benzaldoximino-N-(,B-hydroxyethyl) carbamate Seven grams (0.07 mole) ofphosgene, 8.6 grams (0.07 mole) of N,N-dimethylaniline and 14.5 grams(0.05 moles) of 4-[O-(0,0-diethylphosphorothioyl)] benzaldoxime arereacted in 200 ml. anhydrous diethyl ether by the procedure described inExample 6. The ethereal solution is cooled to 10 C. and a solution of6.1

grams (0.1 mole) of ethanolamine and 10 ml. of water is added at such arate that the temperature does not exceed 15 C. After the addition iscomplete, the mixture is stirred at room temperature for one hour. Theproduct is isolated by the procedure described in Example 6-. There isobtained a 17.8 grams (94.8% of theory) of the title compound, n=1.5423.

EXAMPLE 8 Preparation of 4-[O-(0,0diethylphosphorothioyl)]benzaldoximino N[/3-(N",N-diethylamino)ethyl]carbamate Seven grams (0.07mole) of phosgene, 8.6 grams (0.07 mole) of N,N-di-methylaniline, and14.5 grams (0.05 mole) of 4-[0 (0,0 diethylphosphorothioyl)]benzaldoxime are reacted in 200 ml. of anhydrous diethyl ether by theprocedure described in Example 6. The etherial solution is washed with100 m1. of ice cold 1 N HCl and returned to the reaction flask where itis stirred and cooled to 10 C. A solution of 11.6 grams (0.1 mole) of,8-N,N-diethyl ethylenediamine and 10 ml. of water is added to theetherial solution solution at such a rate that the temperature does notexceed 15 C. After the addition is complete, the mixture is stirred atroom temperature for one hour. An additional 100 ml. of anhydrousdiethyl ether is added, and the mixture is Washed with ml. of ice cold 1N NaOI-I followed by two 50 ml. portions of water. The ether phase isdried with anhydrous MgSO. and evaporated. There is obtained 11.3 grams(51.8% of theory) of the title compound, n =l.5310.

The following is a table of the compounds prepared according to theaforedescribed procedures. Compound numbers have been assigned to eachcompound and are then used for identification throughout the balance ofthe application.

TABLE I /P Y R R1 X Y Q. (1 2 111) CgH5O s 0 H 3 H 1. 5464 C11150 8 O H4 H 1. 5520 CgHsO S 0 H 3 H 1. 5390 CzHsO S O H 4 H 3 94-96 021150 B 0 H4 H 1. 5430 C H5O S 0 H 2 H 1. 5406 CzH O S 0 H 4 H 1. 5318 021150 S 0 H2 H 1. 5354 CzHaO S O H 2 H 1. 5330 021150 8 O H 4 H 1. 5265 CzH O S 0 H2 H 1. 5458 01130 S 0 H 4 H 1. 5655 CH3O S 0 H 4 H 1. 5538 C1130 S O H 3H 1. 5494 CH3O s 0 H 3 H 1. 5400 01130 S O H 3 H 1. 5247 CH3) 5 0 H 4H 1. 5427 021150 B O Z-CHaO 4 H 1. 5410 C2H5O S O Z-CHaO 4 H C (O)NHCH: 1. 5436 0 11 0 B O Z-CHsO 4 H C(O)NHCH2CH=CH2 1. 5303 (111 0 S 02-CH3O 4 H 1. 5586 01130 S O 2 CHaO 4 H C(O) NHCHs. 1. 5510 021350 8 0 3H3 1. 5348 C1130 S O 2-CH30 4 H C (0)NH-phenyl 1. 5670 01130 S o Z'CHZO4 H 1. 5328 021150 B O H 3 CH3 )0 CzH 1. 5094: CzH5O S O H 3 CH: C(O)NHCH3- 1 5340 CHQO S 0 H 4 CH3 1. 5592 CHaO S O H 4 CH: C (O)NHC 1.5527 011150 S 0 H 4 H3 1. 5393 021350 S 0 H 4 3 P (0 QHIQZ CgHsO S 0 H 4CH3 C(O)NHCH3 1. 5382 021150 S 0 H 4 CH3 C(O)NHCH(CH 1. 5263 (31130 S OH 3 CH3 C(O NHCHa 1. 5195 CHBO S 0 H 3 CH: 1. 5128 021150 S 0 H 4 CH3 1.5163 CH30 S 0 4-131 2 H 1. 5665 C1130 S 0 4-131 2 H 1. 5378 (321 8 04-Br 2 H 1. 5486 CHQO S O 4-BI 2 H 1. 5543 CZHQO S 0 4-31 2 H 1. 5410CzHsO S O G-NO: 2 H 1. 5413 See footnotes at end of table.

TABLE IContinued M.p., Compound C.) number R1 X Y Q (p) R2 R3 m) S O H 4CH C(O)N(CH2CH2OCH3)2 1. 5289 S O H 4 H C (O; NH cyolohexyl. 1. 5355 B O(l-CH; 4 CH 1. 5272 S O H 4 H S O H 4 H S 0 H 4 H S 0 H 4 H S O H 4 H SO H 4 CH 5 O H 4 H S O H 4 CH3 S O H 4 CH 8 0 H 4 CH; S O H 4 H S O H 4H S 0 H 4 CH; s 0 H 4 OH; C(O)CC]3 S 0 2-01 4 H C (O)NH-3-C1-phenyl 1.5723 S 0 H 4 CH3 C(O)-lZ-C4Hn 1. 5147 S 0 H 4 H C (O) NHC H 1. 5282 S 0H 4 H C(O)NH-3,4-di-Cl-phen 1.5720 S O H 4 H C (O)NH-4-Br-phenyl 116-118S O H 4 CH3 C(O)NH-4-(CsH11)-.- 1.5216 S O H 4 H O (O)NH (CH C (0) OC2Hu- 1. 5253 S O H 4 H C (O)NH-4-CH S-phenyl 1. 5832 S O H 4 HC(O)NH2 1. 5666 S O H 4 H C (O)N (CHM 97-99 S 0 3-011; 4 CH: C (O) N(i-CaH1) 1. 5169 S O 3-OH3 4 CH: C(O)NH(CHzCH=CHz) 1. 5293 S 0 3-011: 4CH3 (0) 2 1. 5312 S O 3-CHa 4 CH3 1. 5270 S O H 4 H 1. 6090 S O H 4 H 1.5425 S O H 4 H S O 3-CH3 4 CH3 1. 5574 S O 3-0113 4 CH3 1. 5186 S 03-CH: 4 CH3 1. 5128 S O H 4 H 1. 5564 S O H 4 H 1. 5777 S O H 4 HNH-3-CHaS-p 1. 6105 S O H 4 H C(O)NH-4-Br-pheny1. 1. 5998 S O H 4 HC(O)NH-4-Br-phenyl 9499 S O H 4 H C (O)NH (1-C H1) 1. 5274 S O H 4 H C(O) CHzS-4-C1 phenyl 1. 6077 S O H 4 H C (O) CHzS-4-C1- 1.5703 8 O H 4H 1. 5358 S O 3-NO 4 H 1. 5455 S O H 4 CH: 1. 5752 S O 3-N0z 4 H 1. 5833S O S-NO: 4 H 1. 5463 S O H 4 CH! 1. 5493 S O H 4 CH: 1. 5632 S O H 4H 1. 5507 l Semi-solid. Waxy solid.

2 (p)"=posltion of phenyl substitution by [-4 =N0-R3] relative to thephosphorus containing group.

HERBICIDAL SCREENING TESTS Novel compositions are phytotoxic compoundswhich are useful and valuable in controlling various plant species.

In the method of the present invention for controlling undesirableplants which comprises applying an herbicidally eifective amount of theabove-described compounds to the area in which control is desired, anherbicide is used to mean a compound which controls or modifies thegrowth of plants. 'By an herbicidally eflective amount is mean an amountof compound which causes a modifying eflect upon the growth of plants.Such modifying etfects include all deviations from natural development,for example, killing, retardation, defoliation, desiccation, regulation,stunting, tillering, stimulation, dwarfing and the like. By plants it ismeant germinant seeds, emerging seedings, and established vegetationincluding the roots and above-ground portions.

The compounds of this invention were tested as herbicides in thefollowing manner.

Pro-emergence herbicide test.The seeds of crab grass (CG) (Digitariasanguinalis (L.) Scop.), foxtail (Ft) (Setaria gluca (L.) Beauv.),watergrass (WG) (Echinochloa crusgalli (L.) Beauv.), pigweed (PW)Amaranthus retroflexus (L.), mustard (Md) (Brassica iuncea (L.) Coss.),and curly dock (CD) (Rumex crispus (L) were planted in individual rowsone-half inch deep in Santa Cruz sand loam soil contained in compressedpaper flats 8%" x 6 /2", which are 2%" deep. Enough seeds were plantedto give about thirty to fifty plants of each of the weed species in eachflat. The flats were watered after planting. The following day each flatwas sprayed at the rate of 20 pounds of the candidate compound undertest in gallons of solution per acre. An atomizer was used to spray thesolution on the soil surface. The flats were placed in a greenhouse at80 F. and watered regularly. Two weeks later the degree of weed controlwas determined by comparing the amount of germination and growth of eachweed in the treated flats with weeds in several untreated control flats.The results of this test are reported in Table II.

Post-emergence herbicide test.--The seeds of four weed species, crabgrass (CG) (Digitaria sanguinalis (L.) Scop.), watergrass (WG)(Echinochloa crusgali (L.) Beauv.), red oats (R0) (Avena sativa (L.)),mustard (Md) (Brassica juncea (L.) Coss.), and one crop, pinto beans(PB) (Phaseolus vulgaris) were planted in individual rows as describedin the pre-emergence test, supra. Twoweeks after planting, the plantfoliage was sprayed with a 0.5% solution of the test compounds at a rateequivalent to 12.5 pounds/ acre. The treated plants were placed back inthe greenhouse. Injury ratings were recorded 14 days after treatment.The rating system is the same as that used in the pre-emergence test.Table III lists the results obtained therefrom.

TABLE IL-PRE-EMERGENT HERBICIDE TEST Compound number G Ft W G PW Mt CD*Herbicidal activity rating:

+=slight injury. ++=moderate injury. +++=severe injury or death.

TABLE IIL-POST-EMERGENT HERBICIDE TEST Compound number Md Herbieidalactivity rating:

+=slight injury. ++=moderate injury. +++=severe injury or death.

The compounds of the present invention are used as pre-emergence orpost-emergence herbicides and are applied in a variety of ways atvarious concentrations. In practice, the compounds are formulated withan inert carrier, utilizing methods well known to those skilled in theart, thereby making them suitable for application as dusts, sprays, ordrenches and the like in the form and manner required. The mixtures canbe dispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil and water, water in oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. The amount applied depends upon the nature of theseeds or plants to be controlled and the rate of application varies from1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention are applied to the plantsin the conventional manner, Thus, the dust and liquid compositions canbe applied to the plant by the use of power-dusters, boom and handsprayers and spray-dusters. The compositions can also be applied fromairplanes as a dust or a spray because they are effective in very lowdosages. In order to modify or control growth of germinating seeds oremerging seedlings, the dust and liquid compositions are applied to thesoil according to conventional methods and are preferably distributed inthe soil to a depth of at least /2-i11ch below the soil surface. It isnot necessary that the phytotoxic compositions be admixed with the soilparticles and these compositions can be applied merely by spraying orsprinkling the surface of the soil. The phytotoxic compositions of thisinvention can also be applied by addition to irrigation water suppliedto the field to be treated. This method of application permits theenetration of the C0111- positions into the soil as the water isabsorbed therein. Dust compositions granular compositions or liquidformulations applied on the surface of the soil can be distributed belowthe surface of the soil by conventional means such as discing, draggingor mixing operations.

The phytotoxic compositions of this invention can also contain otheradditaments for example, fertilizers, pesticides and the like, used asadjuvant or in combination with any of the above-described adjuvants.Phytotoxicants useful in combination with the above-described compoundsinclude for example 2,4-dichlorophenoxyacetic acids,2,4,S-trichlorophenoxyacetic acid, 2-methyl-4- chlorophenoxyacetic acidand the salts, esters and amides thereof; triazine derivatives, such as2,4-bis(3-methoxypropylamino) 6 methylthio-S-triazine; 2 chloro-4-ethylamino 6 isopropylarnino-S-triazine, and 2ethylamino-4-isopropylamino 6 methylmercapto-S-triazine; ureaderivatives, such as 3-(3,4-dichlorophenyl)-l,1-dimethyl urea and3-(p-chlorophenyl)-1,l-dimethyl urea, and acetamides such asN,N-diallyl-u-chloroacetamide, N-(a-chloroacetyl)hexamethylene imine,and N,N-diethyl-a-bromoacetamide, and the like; benzoic acids such as3-amino-2,S-dichlorobenzoic and; thiocarbonates, such as S-propyldipropylthiocanbonate; S-ethyldipropylthiocarbamate,S-ethyl-cyclohexylethylthiocarbamate, S-ethylhexahydro-lg-azepine-l-carbothioate and the like. Fertilizers useful incombination with the active ingredients include, for example, ammoniumnitrate, urea and superphosphate. Other useful additaments includematerials in which plant organisms take root and grow such as compost,manure, humus, sand and the like.

The compositions of the present invention were tested as foliagefungicides. This test indicated protectant action against fungiattacking plant foliage. Pinto bean plants were sprayed with threeconcentrations of dissolved or suspended chemical in Water, 1000, 500and parts per million (p.p.m.). The active compound was dissolved in anappropriate solvent and further dispersed in water, and for this purposea surface active agent or wetting agent was employed to facilitateformulation of the dispersions. After the sprayed plants were dried,they were inoculated with powdery mildew spores (Erysiphe polygoni).Results were read when disease symptoms were distinct on untreated beanplants. Compound numbers 84 and 86 exhibited 75-99% control at 100p.p.m., and compound number 85 exhibited 100% control at 100 p.p.m. ofthe powdery mildew infection with no phytotoxicity.

Insecticidal evaluation tests The following insect species weresubjected to evaluation tests for insecticidal activity:

(1) Housefiy (H'F)-Musca domestica (Linn.)

(2) German roach (GR)Blattellw germanic'a (Linn) (3) Salt-marshcaterpillar (SMC)--Estigme'ne acrea (Drury) (41) Milkweed Bug(-MWB)ncopeltus fasciatus (Dal- (5) Lygus bug (LB)-Lygus hesparus(Knight) Aliquots of the toxicants, dissolved in an appropriate,solvent, were diluted in water containing 0.002% of a wetting agent,Sponto 221 (a polyoxyether of alkylated phenols blended with organicsulfonates). Test concentrations ranged from 0.1% downward to that atwhich 50% mortality was obtained. In the tests, for these species,one-month old nymphs of the German Cockroach and Lygus Bug and two-weekold nymphs of milkweed bug were placed in separate circular cardboardcages sealed on one end with cellophane and covered by a cloth nettingon the other. Test concentrations for the Lygus Bug ranged from 0.05%downward to that at which 50% mortality was obtained. Each of theaqueous suspensions of the candidate compounds were sprayed onto theinsects through the cloth netting by means of a hand spray gun. Percentmortality in each case recorded after 72. hours and the LD valuesexpressed as percent of toxicant in the aqueous spray was recorded.

For testing the salt marsh caterpillar, test solutions were prepared inan identical manner and at concentrations the same as for the Germancockroach and the milkweed bug above. Sections of bitter dock (Rwmexobtusifolus) leaves, 11.5 inches in length were immersed in the testsolutions for 10 to seconds and placed on a wire screen to dry. Thedried leaf was placed on a moistened piece of filter paper in a Petridish and infested with 5 3rd instar larvae. Mortality of the larvae wasrecorded after 72 hours and the LD values are exppressed as percentactive ingredient in the aqueous suspension.

The following procedure was used to test housefiies. A stock solutioncontaining 10 ,ug./ml. of the toxicant in an appropriate solvent wasprepared. Aliquots of this solution were combined with 1 milliliter ofan acetonepeanut oil solution in a glass Petri dish and allowed to dry.The aliquots were there to achieve desired toxicant concentrationranging from 100 ,ug. per Petri dish to that at which 50% mortality wasattained. The Petri dishes were placed in a circular cardboard cage,closed on the bottom with cellophane and covered on top with clothnetting. Twenty-five female houseflies were introduced into the cage andthe percent mortality was recorded after 48 hours. The LD values areexpressed in terms of ,ug. per female flies. The result of theseinsecticidal evaluation tests are given in Table IV.

TABLE IV.(LD o VALUE S) TAB LE IV-Continued Percent Compound number HF CR LB SMO 50 0 .1 0 .01 0 .1 0 .1 0.05 0 .1 50 0.1 0.05 0.1 10 0 .1 0 .050 .1 30 0.1 0.05 0.1 10 0 .1 0.05 0 .1 5 0 .1 0.05 0 .1 10 0.1 0.05 0.120 0 .1 0 .1 3 0 .1 0 .005 0 .1 3 0 .1 0.003 0 .1 8 0 .1 0 .05 0 .05 8 0.1 0 .03 0 .1 8 0 .1 0 .05 0 .08 50 0 .1 0 .05 0 .05 8 0 .1 0.05 0 .03 80 .1 0 .005 0 .05 80 0 .1 0 .0 0 .1 5 0 .1 0 .008 0 .1 8 0 .1 0.05 0 .150 0.1 0.05 0.1 10 0 .1 0.05 0 .1 0.1 0 .05 0 .1 2 .5 0 .01 0 .005 0 .010 .8 0 .005 0 .001 0 .01 1 .5 0 .01 0 .001 0 .03 10 0 .1 0 .1 30 0.1 0.130 0 .1 0 .1 30 0 .1 0 .1 30 0 .1 0 .1 4 0.05 0.05 8 0 .05 0.08 8 0 .10. 1 15 0. 1 0. 03 0. 1 40 0. 1 0. 05 0. 1 50 0.1 0. 05 0. 1 30 0. 1 0.05 0. 1 7 0. 1 0. 03 0. 05 8 0. 1 0. 03 0. 05 5 0. 1 0. 005 0. 1 8 0. 10. 01 0. 05 7 0. 1 0. 05 0. 1 8 0. 1 0.05 0. 1 2. 5 0. 05 0. 005 0. 01 60. 03 0. 008 0. 05 7 0. 03 0. 01 0. 005 7 0. 03 0. 01 0. 008 3 0. 03 0.005 0. 003 7 0. 03 0. 01 0. 005 3 0. 03 0. 008 0. 1 6 0. 08 0. 01 0. 1 70. 1 0. 03 0. 03 7 0. 1 0. 05 0. 1 4 0. 1 0. 005 0. 008 8 0. 1 0. 01 0.03 5 0. 1 0. 01 O. 1 5 0. 05 0. 005 0. 01 5 0. 1 0. 008 0. 1 5 0. 03 0.003 0. 01 5 0. 1 0. 05 0. 1 6 0. 1 0. 005 0. 03 5 0. 1 0. 03 0. 01 6 0.03 0. 003 0. 05 4 0. 03 0. 01 0. 03 5 0. 03 0. 03 0. 03 4 0. 08 0. 0080. 05 4 0. 1 0. O3 0. 1 3 0. 05 O. 008 0. 01 6 0. 03 0. 01 0. 001 3 0.03 0. 005 0.03 3 0. 01 0. 005 0. 005 8 0. 1 0. 01 0. 1 9 0. 1 0. 03 0. 15 0. 1 0. 01 0. 1 4 0. 1 0. 005 0. 05 2 0. 03 0. 003 0. 03 7 0. 1 0. 050. 1 8 0. 1 0. 03 0. 05

In testing against milkweed bug representative LD results obtained werefor compound numbers 47, 55 and 560.01%; for compound numbers 49, 67 and143 0.03%; compound number 640.05%; compound number 68-0.08% andcompound number 540.008%.

Compound number 55 is extremely useful in the control of European cornborer (Pyrausta nubilalis (Hiibner)).

The same test procedure as mentioned above for salt marsh caterpillarwas used for cotton bollworm (Heliothis zea (Boddie) except that leavesof Romaine lettuce were utilized as the host plant rather than bitterdock. The following compounds were found to be active against cottonbollworm: the LD values obtained were (5), (54) and (143) 0.005%; (10)0.01%; (13) 0.03%; (137) 0.001%; (55), (138), (141), and '(142) 0.003%;and (56) 0.008%.

The compounds were also found to be active against two-spotted mite(Tetranychus urticae (Koch)). Lima bean plants (Phaseolus sp.) wereutilized as the host plant and infested with 50 to 75 mites of variousages. Twenty four hours after infestation, they were sprayed to thepoint of run off with aqueous suspension of the toxicant. Testconcentrations range from 0.05% to that at which 50% mortality wasobtained. The following compounds exhibited LD values of 0.005% (9) and(56); 0.001% (55) and 0.008% (46).

The compounds were also found to be active against black bean aphid(Aphis fabae (Scop.)). The same test procedure as given for thetwo-spotted mite above was used for black bean aphid except thatnasturtium (Tropaeolum sp.) plants approximately 2 to 3 inches tall wereused as the host plant. The following compounds exhibited LD values of0.005% (40); 0.005 (55);0.003% (37); 0.003% (38);0.003% (65); 0.008%(56); and 0.008% (64).

Animal systemic evaluation tests Candidate test compounds, usuallyformulated in Tween-20 (polyoxyethylene (20) 'Sorbitan monolaurate), areadministered orally by stomach tube at an initial dosage of 400 mg./kg.to fasted male Swiss albino mice. Two hours after treatment, the miceare killed by cervical dislocation and both thighs are dissected fromeach test animal and placed in labeled glass vials. Each vial isinoculated with newly hatched black blow fly larvae (Phormia regina(Meigen)) and stored in an incubator at 80 F. and 45-50% relativehumidity. Tissues from mice that die during the two hour holding periodafter administration of the compounds are processed in the same manner.After the larvae had fed on the tissues for 48 hours, the vials areexamined and the percentage of larvae mortality in each is noted. If 80%or more of the larvae are killed at the initial dosage, successivelylower dosages are then tested until the lowest dosage that killed atleast 80% of the larvae is determined.

In this animal systemic insecticide evaluation test, compounds aretested further on guinea pigs, using the oral route of administration.The compounds are formulated as solutions or suspensions in Tween andadministered at an initial dosage of 100 mg./kg. Twenty-four hours priorto treatment, the guinea pigs are wounded and the wounds infested withlarvae of the black blow fly (Phormia regina (Meigen)). At four andtwenty-four hours after treatment, stable flies (Stomoxys calcitrans(L.)) are fed on the guinea pigs. Engorged flies are held for 24 hoursto see if they are killed by the blood they ingest. At 24 hours aftertreatment, the wounds are examined to see if the fly larvae are killedby the insecticide. If the larvae are alive, they are removed from thewounds. If any of the arthropods are killed at the initial dosage, thecandidate insecticides are administered at lower dosages until there wasno significant insecticidal activity. The following table gives theresults of the mouse assay and guinea pig assay tests described above.

TABLE V.ANIMAL SYSTEMIC INSECTICIDE ACTIVITY Lowest dosage (mg-1 9activity Mouse assay Guinea pig assay agaigst sta e Compound Lethal so%Lethal Blow fly flies (4 number to mice active to G. pig larvae hrs.)

Guinea pig assay Lethal to G. pig

Mouse assay Lethal to mice active Compound number The test resultsindicate that these compounds are biologically active and are useful asanimal systemic insecticides. The compounds can be used as effectiveparasiticides by applying them in a variety of ways and at variousconcentrations, depending upon the nature and habitat of the parasite tobe controlled.

The candidate compounds were employed in an in vitro tick assay. In thistest unfed lone star tick nymphs (Amblyomma americanum (L.)) wereconfined for 24 hours in cotton cloth that had been treated in acetonesolutions of the test compounds. The percentage of nymphal mortality wasthen observed. If 80% or more of the nymphs were killed at the initialscreening level of 1.0% for a given compound, the compound was testedfurther at lower levels. The compounds 5, 11, 17, 20, 23, 26, 31, 33,36, 38, 61, 64 and 65 exhibited 80% or better control of the tick nymphsat 0.5%. Compound number 29 exhibited 80% or better control of the ticknymphs at 0.1% and compound number 32 exhibited 80% or better control at1.0% concentrations. Compound number 28 at a concentration of 0.05 wasbetter than 80% lethal to tick nymphs.

Internal animal parasite systemic tests The following proceduresdescribe the chemoprophylactic and chemotherapeutic efficacy testsutilized to demonstrate the animal arasitology activity of thephosphorus-containing oxime carbamate compositions of the presentinvention.

Test 1.Unparasitized weanling mice were offered medicated food for 1-2days prior to inducing infections, and for a total of 21 days infectionswere administered per os using 100-3 00 embryonated ova/ mouse ofSyphacia obvelata (8.0.) and 100-300 embryonated ova/mouse ofAspiculuris tetraptera (A.t.

A suitable number of unmedicated littermate mice also received the aboveinfection and served as control to determine the comparative efi'icacyof the medications. All mice were sacrificed after 21 days (themedication period) and the residual parasites found in the intestinewere identified and counted. These counts in the medicated groups werecompared to the unmedicated (controls) and a percent eflicacy wasassigned, (M/ ICX100)-100=percent efiicacy.

Test 2.Weanling mice were housed together with older pinworm (S. 0.) and(A. t.) infected mice in a box with damp litter for 15 to 21 days toallow a heavy pin- Worm infection containing all stages of oxyurid (S.0. and A. t.) to naturally build up. At the end of this holding period,the post-weanling littermates were weighed in- 1 7 dividually and dosedwith the subject compounds (suspended in Tween 20) on a body weightbasis. One to 3 days later, these mice were scarificed and the residualworms identified, counted and compared to the unmedicated controls.Examples of efficacy observed for six com- 5 pounds of the present1nvent1on are given in the following table.

TABLE VL-INTERNAL ANIMAL SYSTEMIC ACTIVITY Test Dosa e: Percentefificienc Compound proce- (1) .p.m. or y number dure 2 5 mg./kg. S. o.A. t.

The compounds of the present invention are useful as effectiveinsecticides, herbicides, and external and internal animal parasiticidesand are applicable in a variety of ways at various concentrations. Inpractice, the compounds are formulated with an inert adjuvant utilizingmethods Well known to those skilled in the art, thereby making themsuitable for application and administration as dusts, sprays, drenchesand the like in the form and manner required. The mixtures can bedispersed in water with the aid of a wetting agent or they can beemployed in organic liquid compositions, oil-in-water, water-in-oilemulsions, with or without the addition of wetting, dispersing oremulsifying agents. Administration of said parasiticidal compositions toanimal for systemic control of parasites can be in animal feedstuffswhich contain feed components of such as grain, grasses and the like,and certain beneficial additives such as vitamins, proteins, fats,minerals and carbohydrates. They can be given also in drinking water orskimmed milk, or in the form of tablets or capsules. Further methods ofapplication include sprays, dyes, dips, dermal pour-on, subcutaneousadministration, intramuscular injection and the like. The exact dose tobe administered to the animal is dependent upon the parasite to becontrolled by the particular compound employed, as described herein, asWell as upon whether the administration is to be a single dose or amultiple dose over a period of days. In general, it has been found thatthe systemic parasiticides of this invention can be administered orallyor parenterally to warm blooded animals in amounts ranging from about0.01 to about 600 milligrams per kilogram of body weight.

What is claimed is:

1. A method of controlling insects which comprises contacting saidinsects with an insecticidally effective quantity of a compound havingthe formula 1 -o R R1 =NOR3 in which X is selected from the groupconsisting of oxygen and sulfur;

R is selected from the group consisting of lower alkyl and lower alkoxy,each having from 1 to 6 carbon atoms, inclusive;

R is selected from the group consisting of lower alkyl having from 1 to6 carbon atoms, inclusive, lower alkoxy having from 1 to 6 carbon atoms,inclusive, amino, monomethylamino and phenyl;

Q is selected from the group consisting of hydrogen, di-

valent tetramethylenediene-1,3, lower alkoxy or lower alkyl each havingfrom 1 to 4 carbon atoms, inclusive, nitro, halogen and diethylthionophosphoryloxy;

R is selected from the group consisting of hydrogen, lower alkyl havingfrom 1 to 4 carbon atoms and phenyl;

R is a carbamate in which R and R are each independently selected fromthe group consisting of hydrogen; alkyl having from 1 to 10 carbonatoms, inclusive; substituted alkyl having 1 to 6 carbon atoms,inclusive, said substituent is selected from the group consisting ofhydroxy, halogen, amino, diethyl amino, and methoxy; lower alkenylhaving from 2 to 4 carbon atoms, inclusive; carboalkoxy alkyl having atotal of from 3 to 8 carbon atoms, inclusive; cycloalkyl having from 3to 6 carbon atoms, inclusive; phenyl; naphthyl; substituted phenylwherein said substituents are selected from the group consisting ofhalogen, lower alkyl, lower alkoxy, lower thioalkyl, lower dialkylaminoin which said lower alkyl and lower alkoxy moieties have from 1 to 4carbon atoms, inclusive, nitro, cyano, and trifluoromethyl. 2. Themethod according to claim 1 in which R is C H O, R is C H O, X is S, Qis H and the C(R =NOR group is in the nuclear 4-position in which R is Hand R is C(O)NHCH 3. The method according to claim 1 in which R isC2H50, R1 is C2H50, X iS S, Q is H and the group is in the nuclear4-position in which R; is H and R is C(O)NHCH CH=CH 4. The methodaccording to claim 1 in which R is C H O, R is C H O, X is S, Q is H andthe group is in the nuclear 2-position in which R is H and R is C(O)NHCHCH=CH 5. The method according to claim 1 in which R is C H O, R is C HO, X is S, Q is H and the 19 group is in the nuclear 4-position in whichR is H and R3 is 6. The method according to claim 1 in which R is CH O,R is CH O, X is S, Q is H and the C(R )=NOR group is in the nuclear4-position in which R is H and R is C(O)NHCH(CH 7. The method accordingto claim 1 in which R is CH O, R is CH O, X is S, Q is H and the C(R=NOR group is in the nuclear 4-position in which R is CH and R isC(O)NHCH 8. The method according to claim 1 in which R is C H O, R is CH O, X is S, Q is H and the C(R =NOR group is in the nuclear 4-positionin which R is CH and R is C(O) NHCH 9. The method according to claim 1in which R is C H O, R is C H O, X is S, Q is H and the group in thenuclear 4-position in which R is CH and R is C(O)NHCH(CH 10. The methodaccording to claim 1 in which R is C H 0, R is C H X is S, Q is H andthe C(R )=NOR group is in the nuclear 4-position in which R is H and Ris C(O)NHCH 11. The method according to claim 1 in which R is C H O, Ris C H X is S, Q is H and the C(R =NOR group is in the nuclear4-position in which R is H and R is C(O)NH-3-chloro-phenyl.

12. The method according to claim 1 in which R is C H O, R is 1-1 X isS, Q is H and the C(R2) =NOR group is in the nuclear 4-position in whichR is H and R is C(O)NHCH CH=CH 13. The method according to claim 1 inwhich R is C l-I 0, R is C H O, X is S, Q is H and the C(R =NOR group isin the nuclear 4-position in which R is H and R is C(O)N(CH 14. Themethod according to claim 1 in which R is C H O, R is C H O, X is S, Qis 2-Cl and the C(R =NOR group is in the nuclear 4-position in which Ris H and R3 is C(O)NH-i-C5H11.

15. The method according to claim 1 in which R is C H O, R is C l-I 0, Xis S, Q is 2-Cl and the C(R =NOR group is in the nuclear 4-position inwhich R is H and R is C(O) NHC H 16. The method according to claim 1 inwhich R is C H R is i-C H O, X is S, Q is H and the C(R =NOR group is inthe nuclear 4-position in which R is H and R is C(O)NHCH 17. The methodaccording to claim 1 in which R is C H R is i-C H O, X is S, Q is H andthe C(R =NOR is in the nuclear 4-position in which R is H and R isC(O)NHCH CH=CH 18. The method according to claim 1 in which R is C H Ris i-C H O, X is S, Q is H and the C(R =NOR group is in the nuclear4-position in which R is H and R is C(O)NH-3-chloro-phenyl.

19. The method according to claim 1 in which R is C2H50, R1 is C2H50, Xis S, Q is 2-CH3O and the =NOR group is in the nuclear 4-position inwhich R is H and R is C(O)NHCH 20. The method according to claim 1 inwhich R is C H O, R is C l-I 0, X is S, Q is H and the C(R =NOR group isin the nuclear 4-position in which R is CH, and R is C(O)NHC H -n.

21. The method according to claim 1 in which R is C2H50, R1 is C2H50, Xis S, Q is 3'CH3 and the =NOR group is in the nuclear 4-position inwhich R is CH3 and R3 is NHC4H9.

22. The method according to claim 1 in which R is C2H5O, R1 is C2H50, Xis S, Q is H and the group is in the nuclear 4-position in which R is Hand R is C(O)NH-3-chloro-4methyl phenyl.

23. The method according to claim 1 in which R is C2H50, R1 is C2H50, Xis S, Q is H and the 20 group is in the nuclear 4-position in which R isH and R is C(O)NH-t-C H 24. The method according to claim 1 in which Ris C H O, R is C H O, X is S, Q is H and the C(R =NOR group is in thenuclear 4-position in which R is H and R is C(O)NH-phenyl.

25. The method according to claim 1 in which R is C H O, R is C H O, Xis S, Q is H and the C(R =NOR group is in the nuclear 4-position inwhich R is H and R is C O NH-4-chloro-3-methylphenyl.

26. The method according to claim 1 in which R is C H O, R is C H X isS, Q is H and the C(R =NOR group is in the nuclear 4-position in which Ris H and R is C(O)NH-cyclohexyl.

27. The method according to claim 1 in which R is C H O, R is C H O, Xis S, Q is H and the C(R2) =NOR group is in the nuclear 4-position inwhich R is H and R is C(O) NH(N,N-diethylaminoethyl) 28. The methodaccording to claim 1 in which R is C2H50, R1 is C2H50, X is S, Q is Hand the group is in the nuclear-4-position in which R is H and R is C(O)NH-3-methylthiophenyl.

29. The method according to claim 1 in which R is 0 1 1 0, R is 0 11 0,X is s, Q is 2-c1 and the C(R =NOR group is in the nuclear 4-position inwhich R is H and R is C(O)NH-3-chlorophenyl.

30. The method according to claim 1 in which R is C2H50, R1 is C2H50, Xis S, Q is H and the group is the nuclear 4-position in which R is H andR is C(O)NHCH C(O)OC H 31. The method according to claim 1 in which R isCH O, R is CH O, X is S, Q is 4-Br and the C(Rz): NOR group is in thenuclear 2-position in which R is H and R is C(O)NHCHg.

32. The method according to claim 1 in which R is CH O, R is CH O, X isS, Q is 4-Br and the C(R =NOR group is in the nuclear 2-position inwhich R is H and R is C(O)NHCH(CH 33. The method according to claim 1 inwhich R is C H O, R is C H O, X is S, Q is 4-Br and the C(R =NOR groupis in the nuclear 2-position in which R is H and R is C(O)NHCH 34. Themethod according to claim 1 in which R is C2H50, R1 is C2H5O, X is S, Qis 4-BI' and this =NOR group is in the nuclear 2-position in which R isH and R is C(O)NHCH 35. The method according to claim 1 in which R is CH O, R is C H O, X is S, Q is H and the C(Rg) =NOR group is in thenuclear 4-position in which R is CH and R is C(O)NHCH 36. The methodaccording to claim 1 in which R is C H R is i-C H O, X is S, Q is H andthe C(R =NOR group is in the nuclear 4-position in which R is H and R isC (O NH-4-bromophenyl.

37. The method according to claim 1 in which R is C H O, R is C H O, Xis S, Q is 2-CH and the C(R =NOR group is in the nuclear 4-position inwhich R is CH and R is C(O)NHCH(CH 38. The method according to claim 1in which R is C H O, R is NH X is S, Q is H and the C(R =NOR group is inthe nuclear 4-position in which R is H and R is C(O)NHCHg- ReferencesCited UNITED STATES PATENTS 2,816,128 12/1957 Allen 260920 ALBERT T.MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner US. Cl. X.R.

